CN101061062A - Method for producing metal oxide film - Google Patents

Method for producing metal oxide film Download PDF

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Publication number
CN101061062A
CN101061062A CNA2005800384833A CN200580038483A CN101061062A CN 101061062 A CN101061062 A CN 101061062A CN A2005800384833 A CNA2005800384833 A CN A2005800384833A CN 200580038483 A CN200580038483 A CN 200580038483A CN 101061062 A CN101061062 A CN 101061062A
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oxide film
metal oxide
solution
metal
manufacture method
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CN101061062B (en
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小堀裕之
大川晃次郎
野村圭介
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Abstract

Disclosed is a method for producing a metal oxide film directly on the surface of a base without catalyzing the base surface. This method enables to produce a uniform metal oxide film by a simple process even when the base has a structured portion. Specifically disclosed is a method for producing a metal oxide film wherein a metal oxide film is obtained by bringing a metal oxide film-forming solution, in which a metal salt or a metal complex is dissolved as the metal source, into contact with the surface of a base. This method for producing a metal oxide film is characterized in that the metal oxide film-forming solution contains a reducing agent.

Description

The manufacture method of metal oxide film
Technical field
The present invention relates to a kind of manufacture method of having used the metal oxide film that contains reductive agent to form the metal oxide film of using solution.
Background technology
The known metal oxides film demonstrated various good rerum naturas in the past, thereby was effectively utilized its characteristic, was used for broad field such as nesa coating, optical thin film, electrolyte fuel cells.Manufacture method as this kind metal oxide film, for example can enumerate sol-gel method, sputtering method, CVD method, PVD method, print process etc., yet because these methods all need to burn till or high vacuum state, device is maximized, thereby complicated and so on the problem of cost height, operability is arranged.
In addition, as other problem of the manufacture method of metal oxide film, can enumerate and be difficult on base material, be provided with the even metal oxide film with structure portion.For example, in sputtering method, consider, lack product having shape-following-up properties, in addition, in print process, be difficult to be implemented in film forming than in the littler structure portion of ceramic particle contained in the black liquid from its principle.In addition, even be considered in the CVD method better aspect product having shape-following-up properties, though for simple shape and more shallow groove etc. can be brought into play effect, the groove structure for complexity is difficult to be provided with the even metal oxide film.
At this kind problem, proposed directly to make the soft solution operation (non-patent literature 1) of metal oxide film at base material from solution.Therefore this kind soft solution operation can solve the problems such as maximization of described device owing to do not need to burn till or high vacuum state usually.In addition, contact with solution because base material and metal oxide film are formed, even so have a base material of the structure portion of complexity, described solution also easily in the intrusing tectonics portion, can obtain the even metal oxide film.
As the trial that has utilized this kind soft solution operation, for example in patent documentation 1, announcing has following method, promptly, by between the anode and negative electrode of the voltage that has been applied in regulation, flow through the reaction soln of the formation element that contains the film that will form to some extent with the flow of regulation, form film.In patent documentation 1,, do not contain reductive agent though in described reaction soln, contain oxygenant.In addition, substrate is limited to electrical conductor, and the membranous of the film of gained is the thick film of corpuscular property.
In addition, for example in patent documentation 2 and patent documentation 3, announcing has following method, that is, the base material that uses Ag catalyzer or Pd catalyzer to carry out catalysis thinner processing be impregnated in zinc oxide separate out in the solution, utilizes the non-electric field method to form the zinc oxide mulch film.In these patent documentations, though used reductive agent such as dimethyamine borane, handling as essential integrant with the catalysis thinner of base material, is not the method that directly forms metal oxide film at substrate surface.In addition, to consider also that with the purposes difference of metal oxide film, the dissatisfactory situation of employed metal in the catalyzer in addition, is handled owing to carry out the catalysis thinner, therefore also has the problem of complex proceduresization.
Non-patent literature 1: resource and material Vol.116p.649-655 (2000)
Patent documentation 1: No. the 3353070th, patent
Patent documentation 2: the spy opens the 2000-8180 communique
Patent documentation 3: the spy opens the 2000-336486 communique
Summary of the invention
The present invention finishes in view of described problem, its main purpose is, a kind of manufacture method of metal oxide film is provided, be substrate surface catalysis thinner not to be handled ground directly forms the metal oxide film of metal oxide film on substrate surface manufacture method, even have at base material under the situation of complicated structure portion, also can obtain the even metal oxide film with easy operation.
In order to solve described problem, the invention provides a kind of manufacture method of metal oxide film, be by making the metal oxide film that has dissolved metal-salt or metal complex as source metal form the manufacture method that obtains the metal oxide film of metal oxide film with solution contact substrate surface, it is characterized in that described metal oxide film forms and contains reductive agent with solution.
According to the present invention, by being formed, described metal oxide film contains reductive agent with solution, and just can substrate surface catalysis thinner not handled ground and on substrate surface, directly form metal oxide film.Because described reductive agent produces electronics in decomposing, therefore can bring out the electrolysis of water, the hydroxide ion that is generated rises the pH of described solution, can become the environment of easy formation metal oxide film.
In addition, according to the present invention, owing to be to contact with solution by described base material is formed with described metal oxide film, directly obtain the manufacture method of metal oxide film by described solution, therefore do not need to burn till or processing such as high vacuum, operation is easy, can realize cost degradation.In addition, even owing to have at base material under the situation of complicated structure portion, described solution also easily in the intrusing tectonics portion, therefore has the advantage that can obtain the even metal oxide film.
In addition, in the described invention, in described substrate surface and described metal oxide film being formed contact with solution, best mixed oxidization gas, wherein, preferred oxygen of described oxidizing gas or ozone.This is because by mixed oxidization gas, can improve the film forming speed of metal oxide film.
In addition, in the described invention, in described substrate surface and described metal oxide film being formed contact with solution, best irradiation ultraviolet radiation.This be because, by irradiation ultraviolet radiation, can bring out electrolytic reaction that is equivalent to water or the decomposition that promotes reductive agent, utilize the hydroxide ion that is produced, the pH that described metal oxide film is formed with solution rises, and becomes the environment of easy formation metal oxide film.In addition, by irradiation ultraviolet radiation, can also improve the crystallinity of the metal oxide film of gained.
In addition, in the described invention, described metal oxide film forms and preferably contains at least a metallic element that is selected from the group that is made of Mg, Al, Si, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Ag, In, Sn, Ce, Sm, Pb, La, Hf, Sc, Gd and Ta with source metal used in the solution.Because described metallic element has regions of metal oxides or metal hydroxides zone in the Pourbaix line chart, therefore be suitable for main composition element as metal oxide film.
In addition, in the described invention, described metal oxide film forms and preferably contains at least a ion species that is selected from the group that is made of chlorate ions, high chloro acid ion, chlorous acid ion, hypochlorite ion, bromic acid ion, hypobromous acid ion, nitrate ion and nitrite ion with solution.This be because, described ion species by with electron reaction, can produce hydroxide ion, the pH that metal oxide film is formed with solution rises, and becomes the environment of easy formation metal oxide film.
The present invention plays following effect, promptly, can substrate surface catalysis thinner not handled ground and on substrate surface, directly form metal oxide film,, also can obtain the even metal oxide film with easy operation even have at base material under the situation of complicated structure portion.
Description of drawings
Fig. 1 is the explanatory view of an example of film formation reaction of the manufacture method of expression metal oxide film of the present invention.
Fig. 2 is the graph of a relation (Pourbaix line chart) of expression with respect to the relation of the pH of cerium and current potential.
Fig. 3 is the explanatory view of an example of the manufacture method of expression metal oxide film of the present invention.
Fig. 4 is the explanatory view of other examples of the manufacture method of expression metal oxide film of the present invention.
Fig. 5 is the explanatory view of other examples of the manufacture method of expression metal oxide film of the present invention.
Fig. 6 is the explanatory view of other examples of the manufacture method of expression metal oxide film of the present invention.
Wherein, 1 ... metal oxide film forms and uses solution, 2 ... base material, 3 ... the cerium oxide film, 4,5 ... roller, 6 ... pump, 7 ... ultraviolet ray
Embodiment
To the manufacture method of metal oxide film of the present invention be elaborated below.
The manufacture method of metal oxide film of the present invention is by making the metal oxide film that has dissolved metal-salt or metal complex as source metal form the manufacture method that obtains the metal oxide film of metal oxide film with solution contact substrate surface, it is characterized in that described metal oxide film forms and contains reductive agent with solution.And so-called " substrate surface " is meant the most surperficial of base material among the present invention, is not meant to utilize catalyst layer that catalysis thinner processing etc. obtains etc. on base material.In addition, the most surperficial upside or downside or the horizontal side that not only refers to reach porous substrate of the what is called of the base material in the porous substrate, but also reach inner.By metal oxide film is contacted with described substrate surface, directly form metal oxide film at substrate surface, just can make manufacturing process more easy.In addition, the what is called among the present invention " metal complex " comprising: for metallic ion coordination inorganics or organic material; The so-called organometallic compound that perhaps in molecule, has the metal-carbon key.
Among the present invention, for example can give nonmetallic character to the metal base of having implemented microfabrication.Specifically, can enumerate the way of giving insulativity, compare, can at high temperature use with the insulating method that utilizes resin to realize in the past.In addition, the metal oxide film that utilizes the manufacturing of this kind method is because good, fine and close with the connecting airtight property of metal base, therefore need the thickness about 10 μ m different with in the past the insulating method that utilizes resin to realize, even the metal oxide film of the thickness about 1 μ m also can obtain equal insulativity.
In addition, among the present invention, for example can give erosion resistance to the metal base of having implemented microfabrication.Specifically, strong by making acid or alkali tolerance, the metal oxide film that has electroconductibility in addition just can obtain following member, that is, even if at metal just then in the environment that can't use, also can use.In addition, among the present invention, owing to can obtain the described coloring metal oxide film that has possessed erosion resistance, therefore also can be used for the member of requirement designability, the strick precaution acid rain that can be used for buildings or equipment (plant) specifically is with member etc.
In addition, the present invention also goes for having implemented in the resin base material etc. of microfabrication.Because the application of the invention, the resin microfabrication that cheapness can be processed easily, give organic solvent resistance, wetting ability, biocompatible, therefore can be used for organic solvent equipment, organic solvent container, biochip, physics and chemistry machine all sidedly.
In addition, because the present invention compares with the manufacture method of in the past metal oxide film, can obtain metal oxide film at low temperatures, therefore can use nonrefractory property base materials such as resin or paper, for example, can bring into play the ability that is suitable for widely for the electronics of continuous miniaturization, incorporate energy relevant device, continuous diversified biological field etc.
For the mechanism of the manufacture method of this kind metal oxide film of the present invention, use following situation to describe, that is, use cerous nitrate (Ce (NO as source metal 3) 3), use borine-dimethyl amine complex compound (another name: dimethyamine borane DMAB), form cerium oxide (CeO as reductive agent 2) film.
Though not clear and definite as yet, described cerium oxide film is considered to utilize 6 following formulas to form.
(i) Ce(NO 3) 3→Ce 3++3NO 3 -
(ii) (CH 3) 2NHBH 3+2H 2O→BO 2 -+(CH 3) 2NH+7H ++6e -
(iii)2H 2O+2e -→2OH -+H 2
(iv) Ce 3+→Ce 4++e -
(v) Ce 4++2OH -→Ce(OH) 2 2+
(vi) Ce(OH) 2 2+→CeO 2+H 2
To use accompanying drawing to be specifically described for this kind mechanism.At first, shown in Fig. 1 (a), cerous nitrate and DMAB are dissolved in the water as solvent, make metal oxide film and form, base material 2 be impregnated in this solution with solution 1.At this moment, cerous nitrate becomes cerium ion ((i) formula) in the aqueous solution.Next, shown in Fig. 1 (b),, and discharge electronics because of reductive agent DMAB decomposes ((ii) formula).Thereafter, shown in Fig. 1 (c), the electronics that is discharged brings out the electrolysis ((iii) formula) of water, produces hydroxide ion, and the pH that metal oxide film is formed with solution rises.Consequently, cerium ion changes valence mumber, and ((iv) formula), ((v) formula) shown in Fig. 1 (d), generates Ce (OH) with the hydroxide ion reaction that is produced again 2 2+Thereafter, shown in Fig. 1 (e), near the Ce (OH) the base material 2 2 2+Because of the rising of partial pH becomes CeO 2((vi) formula).Like this, by repeat (ii)～(the vi) reaction of formula just can form the cerium oxide film 3 shown in Fig. 1 (f).
In addition, Fig. 2 is the Pourbaix line chart of cerium, and described reaction can be thought, because of the Ce of (i) formula generation 3+Owing to, and reached CeO by the rising of the pH that hydroxide ion caused that in (iii) formula, generates 2The zone.According to this situation, if having the metallic element of identical regions of metal oxides, utilize manufacture method of the present invention, just can make metal oxide film in the same manner.In addition, even have the metallic element in metal hydroxides zone, also can obtain metal oxide film by the heating of metal hydroxide film.And, can think among the present invention, even, be not to use water, and be to use in alcohol, the organic solvent etc. as solvent, utilize with reaction or solvent like the described response class in the moisture of contained trace, also can generate metal oxide film.
Below, for the manufacture method of metal oxide film of the present invention, will be elaborated to each formation.
1. metal oxide film forms and uses solution
At first, used metal oxide film formation describes with solution in the manufacture method to metal oxide film of the present invention.Used metal oxide film forms and contains at least with solution among the present invention: reductive agent, as the metal-salt of source metal or metal complex, solvent.
(1) reductive agent
Used reductive agent has following effect among the present invention, that is, utilize decomposition reaction to discharge electronics, utilizes the electrolysis of water to produce hydroxide ion, improves metal oxide film and forms the pH that uses solution.Can promote pH, induce in regions of metal oxides in the Pourbaix line chart or metal hydroxides zone, becomes the environment that is easy to generate metal oxide film.
Form concentration as metal oxide film used among the present invention, though according to the kind of reductive agent and difference as a rule is 0.001～1mol/l, wherein preferred 0.01～0.1mol/l with the described reductive agent in the solution.This is because when concentration is described scope when following, then be difficult to cause the film formation reaction of metal oxide film, enough film forming speeds might can't be obtained, when concentration when described scope is above, then in the effect of gained, can't see significant difference, not ideal enough on cost.
As this kind reductive agent, so long as can be dissolved in the solvent described later, utilize decomposition reaction to discharge the material of electronics, just be not particularly limited, yet for example can enumerate borine-tert-butylamine complex compound, borine-N, N diethylbenzene amine complex, borine-dimethyl amine complex compound, borine-boranes complex compound, hydroxide cyano group boron sodium, boron hydroxide sodium such as Trimethylamine complex compound wherein preferably use the boranes complex compound.
(2) source metal
Used source metal is to be dissolved in metal oxide film to form with in the solution among the present invention, utilizes the material that is used for giving metal oxide film of reductive agent etc.Used source metal among the present invention then both can be a metal-salt so long as be dissolved in material in the solvent described later, also can be metal complex.
Form the concentration of using the described source metal in the solution as metal oxide film used among the present invention, for source metal is the situation of metal-salt, be generally 0.001～1mol/l, wherein preferred 0.01～0.1mol/l, for source metal is the situation of metal complex, be generally 0.001～1mol/l, wherein preferred 0.01～0.1mol/l.This be because, when concentration is described scope when following, then be difficult to cause the film formation reaction of metal oxide film, might can't obtain required metal oxide film, when concentration when described scope is above, then might become throw out.
As the metallic element that constitutes this kind source metal, so long as can obtain required metal oxide film, just be not particularly limited, yet for example can from the group that constitutes by Mg, Al, Si, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Ag, In, Sn, Ce, Sm, Pb, La, Hf, Sc, Gd and Ta, select.Because described metallic element has regions of metal oxides or metal hydroxides zone in the Pourbaix line chart, therefore be suitable for main composition element as metal oxide film.
As described metal-salt, specifically, can enumerate the muriate that contains described metallic element, nitrate, vitriol, perchlorate, acetate, phosphoric acid salt, bromate etc.Wherein, among the present invention, preferably use muriate, nitrate, acetate etc.This is because these compounds obtain easily as universal product.
In addition, as described metal complex, specifically, can enumerate: diethoxy magnesium, aluminium acetylacetonate, the methyl ethyl diketone calcium dihydrate, two (methoxy ethoxy) calcium, the calglucon monohydrate, the citrate of lime tetrahydrate, the calcium salicylate dihydrate, the lactic acid titanium, titanium acetylacetone, tetra isopropyl titanate, the tetra-n-butyl titanic acid ester, four (2-ethylhexyl) titanic acid ester, the butyltitanate dipolymer, two (ethyl six oxidations) two (2-ethyl-3-hydroxyl six oxidations) titanium, diisopropoxy titanium two (trolamine), two (DL-Lactic acid ammonium salt) titaniums of dihydroxyl, diisopropoxy titanium two (methyl aceto acetate), titanium peroxidation ammonium citrate tetrahydrate, ferrocene (II), ironic lactate (II) trihydrate, ferric acetyl acetonade (III), acetylacetone cobalt (II), acetylacetonate nickel (II) dihydrate, acetylacetone copper (II), copper (II) two pivalyl methane (copper (II) dipyvarolylmethanate), ethyl acetoacetic acid copper (II), zinc acetylacetonate, the zinc lactate trihydrate, the zinc salicylate trihydrate, Zinic stearas, strontium two pivalyl methane (strontium dipyvarolylmethanate), yttrium two pivalyl methane (yttrium dipyvarolylmethanate), four n-butoxy zirconiums, oxyethyl group zirconium (IV), zirconium-n-propylate, zirconium-n-butylate, tetrem acyl acetone zirconium, single acetyl acetone zirconium, the two ethyl acetoacetic acid zirconiums of methyl ethyl diketone, zirconium acetate, the Stearinsaeure zirconium, five n-butoxy niobiums, five oxyethyl group niobiums, five isopropoxy niobiums, tri acetylacetonato indium (III), 2 ethyl hexanoic acid indium (III), tin tetraethyl, dibutyltin oxide (IV), thricyclohexyl tin (IV) oxyhydroxide, methyl ethyl diketone lanthanum dihydrate, three (methoxy ethoxy) lanthanum, five isopropoxy tantalums, five ethoxy-tantalum, ethoxy-tantalum (V), methyl ethyl diketone cerium (III) n hydrate, lead citrate (II) trihydrate, cyclohexane butyric acid lead etc.Wherein, among the present invention, preferably use diethoxy magnesium, aluminium acetylacetonate, the methyl ethyl diketone calcium dihydrate, the lactic acid titanium, titanium acetylacetone, tetra isopropyl titanate, the tetra-n-butyl titanic acid ester, four (2-ethylhexyl) titanic acid ester, the butyltitanate dipolymer, diisopropoxy titanium two (ethyl acetoacetic acid), ironic lactate (II) trihydrate, ferric acetyl acetonade (III), zinc acetylacetonate, the zinc lactate trihydrate, strontium two pivalyl methane (strontium dipyvarolylmethanate), five oxyethyl group niobiums, tri acetylacetonato indium (III), 2 ethyl hexanoic acid indium (III), tin tetraethyl, dibutyltin oxide (IV), methyl ethyl diketone lanthanum dihydrate, three (methoxy ethoxy) lanthanum, methyl ethyl diketone cerium (III) n hydrate.
In addition, among the present invention, metal oxide film forms also can contain 2 kinds of the above metallic elements with solution, by using multiple metallic element, for example just can obtain ITO, Gd-CeO 2, Sm-CeO 2, Ni-Fe 2O 3Deng the complex metal oxides film.
(3) solvent
Used solvent among the present invention is so long as can dissolve the solvent of described reductive agent and source metal etc., just be not particularly limited, it for example is the situation of metal-salt for source metal, can enumerate total carbon number such as water, methyl alcohol, ethanol, Virahol, propyl alcohol, butanols at the lower alcohol below 5, toluene and their mixed solvent etc., for source metal is the situation of metal complex, can enumerate water, described lower alcohol, toluene and their mixed solvent.In addition, among the present invention, also described solvent can be used in combination, for example for use low and the metal complex that solvability in organic solvent is high of solvability in water, solvability in organic solvent is low and the situation of the reductive agent that solvability in water is high, can be by water is mixed with organic solvent with both dissolvings, the metal oxide film that forms homogeneous forms uses solution.
(4) additive
In addition, used metal oxide film formation also can contain additives such as assisting ion source or tensio-active agent with solution among the present invention.
Described assisting ion source is the material that produces hydroxide ion with electron reaction, can promote metal oxide film and form the pH that uses solution, becomes the environment of easy formation metal oxide film.In addition, the usage quantity in described assisting ion source is preferably suitably selected to use with used source metal or reductive agent coupling ground.
As this kind assisting ion source, specifically, can enumerate the ion species that is selected from the group that constitutes by chlorate ions, high chloro acid ion, chlorous acid ion, hypochlorite ion, bromic acid ion, hypobromous acid ion, nitrate ion and nitrite ion.Can think that these assisting ion sources cause following reaction in solution.
Figure A20058003848300111
Figure A20058003848300112
Figure A20058003848300114
Figure A20058003848300115
Figure A20058003848300116
Figure A20058003848300117
Figure A20058003848300118
In addition, described tensio-active agent is to act on metal oxide film to form the interface of using solution and substrate surface, has the material that generates the effect of metal oxide film at substrate surface easily.The usage quantity of described tensio-active agent is preferably suitably selected to use with used source metal or reductive agent coupling ground.
Specifically, this kind tensio-active agent can be enumerated Surfinol series such as Surfinol 485, Surfinol SE, SurfinolSE-F, Surfinol 504, Surfinol GA, Surfinol 104A, Surfinol 104BC, Surfinol104PPM, Surfinol 104E, Surfinol 104PA (above complete day letter chemical industry (strain) system that is), NIKKOL AM301, NIKKOL AM313ON (the above full daylight Chemical corporate system that is) etc.
2. base material
Below, base material used in the manufacture method to metal oxide film of the present invention describes.Material as base material used among the present invention is not particularly limited, but for example can use glass, plastics or resin, metal or alloy, semi-conductor or pottery, paper, cloth etc.Purposes of functions such as the erosion resistance that the material of described base material is preferably considered to utilize metal oxide film to give, insulativity, wetting ability, member etc. and suitably selecting.
In addition, though base material used among the present invention is not particularly limited, for example also can be material, material, the material of having offered the hole with microstructure portion with level and smooth surface, carve slotted material, exist stream material, porous materials, possessed the material of porous-film.Wherein, among the present invention, preferred substrates is material, the porous materials with microstructure, the material that has possessed porous-film.This be because, metal oxide film forms with solution can invade inside to these base materials, formation has the metal oxide film of good product having shape-following-up properties.
3. base material and metal oxide film form the contact method with solution
Below, the contact method that the base material in the manufacture method of metal oxide film of the present invention and metal oxide film are formed with solution describes.As the described contact method among the present invention, so long as make described base material form the method that contacts with solution with described metal oxide film, just be not particularly limited, specifically, can enumerate rolling method, pickling process, utilize vane-type method, become vaporific solution and method etc. coating.
For example, rolling method is by making base material 2 by between roller 4 and the roller 5 for example as shown in Figure 3, and on substrate surface the method for formation metal oxide film, be suitable for the manufacturing of successive metal oxide film.In addition, pickling process is to form with in the solution by base material being impregnated in metal oxide film, on substrate surface, form the method for metal oxide film, for example shown in Fig. 4 (a), by base material 2 mass-impregnations are formed with in the solution 1 in metal oxide film, just can form metal oxide film at base material 2 comprehensively.In addition, though in Fig. 4 (a), do not show,, the metal oxide film of pattern-like just can be set on the surface of base material 2 by on the surface of base material 2, shielding portion being set.In addition, for example shown in Fig. 4 (b), form with solution 1, metal oxide film is formed with solution 1 only contact, just can only metal oxide film be set at inner peripheral surface with the inner peripheral surface of base material 2 by flow through metal oxide film with certain flow.In addition, the method for utilizing vane-type is following method, promptly, for example as shown in Figure 5, by utilizing pump 6 metal oxide film is formed with solution 1 circulation, only heated substrate 2, just can promote near the decomposition reaction of the reductive agent that substrate surface is, on substrate surface, form metal oxide film.
In addition, in the manufacture method of metal oxide film of the present invention, in substrate surface and metal oxide film being formed contact with solution, make up by mixed oxidization gas, irradiation ultraviolet radiation, heating or with them, just can improve the film forming speed of metal oxide film.Below will describe these methods.
(1) utilizes the raising of the film forming speed that the mixing of oxidizing gas realizes
Among the present invention, in substrate surface and metal oxide film being formed contact with solution, best mixed oxidization gas.
As this kind oxidizing gas, so long as have the gas of oxidation capacity, can improve the film forming speed of metal oxide film, just be not particularly limited, for example can enumerate oxygen, ozone, nitrous acid gas, nitrogen peroxide, dioxide peroxide, halogen gas etc., wherein preferably use oxygen and ozone, especially preferably use ozone.This is because in industrial easy acquisition, can realize cost degradation.
In addition, blending means as described oxidizing gas, though be not particularly limited, for example under the situation of having used described pickling process, can enumerate the described oxidizing gas that makes air bubble-shaped and form the method that contacts with the contacted part of solution with metal oxide film with substrate surface.Though the importing of the oxidizing gas of this kind air bubble-shaped is not particularly limited, for example can enumerate the method for using bubbler.This be because, by using bubbler, can increase the contact area of oxidizing gas and described solution, can improve the film forming speed of metal oxide film effectively.As this kind bubbler, can use general bubbler, for example can enumerate Naflon bubbler (Asone corporate system) etc.In addition, described oxidizing gas can be supplied with by common air pump, for ozone, can be formed with solution to metal oxide film by ozone generating-device and supply with.
(2) utilize the raising of the film forming speed that ultraviolet irradiation realizes
In addition, among the present invention, in substrate surface and metal oxide film being formed contact with solution, best irradiation ultraviolet radiation.This be because, by irradiation ultraviolet radiation, can bring out electrolytic reaction that is equivalent to water or the decomposition that promotes reductive agent, utilize the hydroxide ion that is produced, the pH that described metal oxide film is formed with solution rises, and becomes the environment of easy formation metal oxide film.In addition, by irradiation ultraviolet radiation, can produce hydroxide ion by described assisting ion source.In addition, by irradiation ultraviolet radiation, can also improve the crystallinity of the metal oxide film of gained.
Ultraviolet irradiation method as the manner, so long as form the method for shining with the contact part of solution to substrate surface and metal oxide film, just be not particularly limited, for example under the situation of using described pickling process, can enumerate following method etc., that is, as shown in Figure 6, base material 2 be impregnated in metal oxide film to be formed with in the solution 1, from solution side irradiation ultraviolet radiation 7.Under this situation, from forming the contact part viewpoint consideration of irradiation ultraviolet radiation correctly of using solution to substrate surface and metal oxide film, the metal oxide film that preferably is present on the illuminated ultraviolet substrate surface forms the thinner thickness of using solution.
In addition, the ultraviolet wavelength as used in the manner is generally 185～470nm, wherein preferred 185～260nm.In addition, the ultraviolet intensity as used in the manner is generally 1～20mW/cm 2, wherein preferred 5～15mW/cm 2
As the UV irradiation equipment of carrying out this kind uviolizing, can use generally at UV light irradiation device of selling on the market or laser excitation device etc., for example can enumerate the HB400X-21 of SEN special light sources corporate system etc.
(3) utilize the raising of heating the film forming speed of realizing
In addition, among the present invention, in substrate surface and metal oxide film being formed contact, preferably heat with solution.This be because, by heating, can promote the decomposition reaction of reductive agent, can improve film forming speed.As the method that heats, so long as can improve the method for the film forming speed of metal oxide film, just be not particularly limited, however the way of wherein preferred heated substrate, preferred especially heated substrate and metal oxide film form the way with solution.This is because can promote near the decomposition reaction of the reductive agent that base material is.
As this kind Heating temperature, preferably suitably select with the used reductive agent or the characteristic matching ground of base material, yet in preferred specifically 50～150 ℃ scope, wherein more preferably in 70～100 ℃ the scope.
4. metal oxide film
Below, the metal oxide film that the manufacture method of utilizing metal oxide film of the present invention is obtained describes.The manufacture method of metal oxide film of the present invention is owing to be to use metal oxide film formation to apply with the wet type of solution, therefore even for example at porous substrate or have under the situation of base materials such as porous insert, metal oxide film forms the inside that also can easily invade porous insert etc. with solution, can obtain the even metal oxide film.
In addition, the metal oxide film that utilizes the manufacture method of metal oxide film of the present invention to obtain can regard as porous substrate, have a porous insert etc. be difficult to obtain stratum basale on the base material of fine and close metal oxide usually, with this metal oxide that forms as stratum basale as nucleus, by the manufacture method of metal oxide film makes described nucleus growth using arbitrarily thereafter, just can on porous insert etc., densification be set and have the metal oxide film of enough thickness.Make the method for nucleus growth as this kind, can use the manufacture method of general metal oxide film, for example can enumerate PVD methods such as vacuum vapour deposition, sputtering method, ion plating method; CVD methods such as plasma CVD, hot CVD, normal atmosphere CVD etc.
And, under the situation of the metal oxide film that the combination of the manufacture method of this kind metal oxide film is obtained have required compactness and thickness, the metal oxide film that utilizes the manufacture method of metal oxide film of the present invention to obtain both can fully cover the surface of base material and become metal oxide film, also base material part ground can be covered.As the metal oxide film that described base material part ground is covered, for example can enumerate situation about existing with island, situation about on level and smooth substrate surface, existing etc. with pattern-like in the inside of porous substrate.
Other
In addition, in the manufacture method of metal oxide film of the present invention, also can utilize the cleaning and the drying of the metal oxide film that described contact method etc. obtains.
The cleaning of described metal oxide film is carried out for the Impurity removal on the surface that will be present in metal oxide film etc., for example can enumerate the use method that used solvent cleans in metal oxide film forms with solution etc.
In addition, the drying of described metal oxide film both can be dry by placing at normal temperatures, also can be in drying in the baking oven etc.
And the present invention is not limited to described embodiment.Described embodiment is an example, for the substantially identical formation of being put down in writing in the scope that has with technical scheme of the present invention of technological thought, serves the same role the mode of effect, no matter is which kind of mode, all is contained in the technical scope of the present invention.
Embodiment
Below, will enumerate embodiment the present invention will be specifically described.
[embodiment 1]
＜the formation of ITO film on the porous alumina particle layer 〉
On glass baseplate, utilize the 20wt% solution of excellent cladding process coating alumina particulate (Micron corporate system, particle diameter 30 μ m), under 500 ℃ temperature, burnt till 2 hours, obtained being provided with the glass baseplate of porous alumina particle layer.
Then, be that 0.03mol/l and tin chloride are among the aqueous solution 1000g of 0.001mol/l to indium chloride, add borine-Trimethylamine complex compound (Northeast chemical company system) as reductive agent, make it to reach 0.1mol/l.In addition,, in described solution, add the 2g sodium chlorate, obtained metal oxide film formation solution as the assisting ion source.
Then, the base material that utilizes described method to obtain was being flooded in described solution 12 hours under 70 ℃ the temperature.At this moment, use solution circulated, make it pass through strainer by described metal oxide film is formed, and with the throw out or the dust eliminating of being sneaked into.Consequently, on described base material, obtained metal oxide film.Thereafter, clean with pure water, drying is 1 hour under 100 ℃, burns till under 350-℃ 1 hour then.
(system of science RINT-1500) has been measured the metal oxide film that utilizes described method to obtain, and its result is to confirm to have formed the ITO film to use the X-ray diffraction device.In addition, (the JEOL corporate system JXA-8900R) has been measured described ITO film, and its result is to confirm that ITO has not only reached porous alumina particle layer surface, and reached inside (glass baseplate contact part) to use the electron rays microanalyser.In addition, can confirm that the porous alumina particle layer is fully covered by the ITO film.
[comparative example 1]
＜utilize the formation of the silicon oxide film on the porous alumina particle layer that the CVD method carries out 〉
Use is provided with the glass baseplate of porous alumina particle layer used among the embodiment 1, uses the CVD method to obtain metal oxide film on the porous alumina particle layer.The condition of CVD method is, applied power is 1.0kW, and the one-tenth film pressure is 40Pa, and the hexamethyldisilazane flow is 40sccm, and oxygen flow is 0.5slm, and film forming substrate surface temperature (film-forming temperature) is 30 ℃.
Use described X-ray diffraction device to measure the metal oxide film that utilizes described method to obtain, its result is to confirm to be formed with silicon oxide film.But, after using described electron rays microanalyser to measure described silicon oxide film, its result is, though have Si oxide on porous alumina particle layer surface, but be not present in porous alumina particle layer inside, do not demonstrate sufficient product having shape-following-up properties.In addition, the porous alumina particle layer is not fully covered by silicon oxide film.
[embodiment 2]
＜in the formation of having implemented the zirconium oxide film on the copper base material of microfabrication 〉
In the present embodiment,, carried out the evaluation of erosion resistance by having implemented to form zirconium oxide film on the copper base material of microfabrication.
At first, in the present embodiment, will utilize etching method to implement the copper (0.5mm is thick) of microfabrication (hole: diameter 1mm, dark 50 μ m, groove: wide 50 μ m, long 10mm, dark 20 μ m) as base material.
Then, in the nitric acid oxidation aqueous zirconium 1000g of 0.03mol/l, add borine-dimethyl amine complex compound (Northeast chemical company system, type number 04886-35), make it to reach 0.1mol/l, obtained metal oxide film formation solution as reductive agent.
Then, described metal oxide film formed to be heated to solution reach 70 ℃ temperature, keeping under 70 ℃ of certain conditions of temperature, use Naflon bubbler (Asone corporate system) to produce the bubble of air.At this moment, use solution circulated, make it by strainer by described metal oxide film is formed, and with the throw out or the dust eliminating of sneaking into.To wherein flooding the described base material 1 hour that has carried out ultrasonic cleaning with neutral detergent, on described base material, obtained metal oxide film.Thereafter, clean with pure water, drying is 1 hour under 80 ℃, burns till under 500 ℃ 1 hour then.
The metal oxide film that utilizes described method to obtain that utilized Visual Confirmation, its result is, on the base material two sides and microfabrication portion confirm to have the film of the degree that can observe interference color.In addition, use described X-ray diffraction device to measure described metal oxide film, its result is that discovery is an amorphous membrance.In addition, utilize photoelectron spectroscopy apparatus (V.G.Scientific corporate system, ESCALAB 200i-XL) to analyze the composition of described metal oxide film, its result is, Zr reaches 30.2Atomic%, and O reaches 64.5Atomic%, can confirm to have formed zirconium oxide film.
[comparative example 2]
＜utilize that pickling process carries out in the formation of having implemented the zirconium oxide film on the copper base material of microfabrication
In this comparative example, with enforcement used among the embodiment 2 copper (0.5mm is thick) in microfabrication (hole: diameter 1mm, dark 50 μ m, groove: wide 50 μ m, long 10mm, dark 20 μ m) as base material.
Then, prepare 10% ethanolic soln of zirconium white particulate (Hosokawa Micron corporate system), utilize the immersion coating method to be coated on the described base material, by utilizing electronics retort furnace (Denken corporate system, P90), under 500 ℃ of temperature, burnt till 2 hours, on described base material, obtained zirconium oxide film.
The zirconium oxide film that utilizes described method to obtain was flooded 24 hours in iodine (with the pure medicine of light) solution, and the result is identical with the base material that is untreated, and can see pitting attack, does not demonstrate sufficient erosion resistance.
[embodiment 3]
＜in the formation of having implemented the oxidation titanium film on the vinylformic acid base material of microfabrication 〉
In the present embodiment, purpose is, by having implemented to form titanium film on the vinylformic acid base material of microfabrication, gives wetting ability.
At first, in the present embodiment, with the vinylformic acid base material (5mm is thick) of the microfabrication (groove: wide 500 μ m, long 100mm, dark 50 μ m) having implemented mechanically to be provided with as base material.
Then, so that water and Virahol (IPA) and toluene reach among 4: 4: 1 the synthetic mixing solutions 1000g of mode, dissolving diisopropoxy titanium two (methyl aceto acetate) (this pharmaceutical industry of pine corporate system), make it to reach 0.1mol/l, then, in this solution, add borine-sulfuration dimethyl complex compound (Northeast chemical company system), make it to reach 0.1mol/l as reductive agent, then in this solution, add the 1g Sodium Nitrite, obtained metal oxide film formation solution.
Then, described base material is remained 80 ℃, under described metal oxide film being formed, use Naflon bubbler (Asone corporate system) to produce the bubble of air, bubble is supplied with to base material with 80 ℃ of certain conditions of solution maintenance temperature.At this moment, use solution circulated, make it by strainer by described metal oxide film is formed, and with the throw out or the dust eliminating of sneaking into.In addition, (SEN special light sources Co., Ltd. system is HB400X-21) with uitraviolet intensity 80mW/cm by this kind base material is used UV irradiation equipment 2Irradiation, and on described base material, obtained metal oxide film., with pure water clean thereafter, dry 1 hour down at 100 ℃.
Use described X-ray diffraction device to measure described metal oxide film, its result is to confirm to have formed described oxidation titanium film.In addition, measured the contact angle of the water of described oxidation titanium film, its result is 25 °, can be confirmed to be wetting ability.And the contact angle of the water of described oxidation titanium film is to obtain according to the result who uses contact angle determination device (consonance interface science (strain) system CA-Z type) to measure (from microsyringe dripped 30 seconds drop after).
[embodiment 4]
In the present embodiment, use SUS, on SUS, formed zirconium oxide film as base material.At first, in the mixed solvent of water 80vol% and Virahol (IPA) 20vol%, chloride oxidation zirconium eight hydrate (ZrCl have been dissolved as source metal 2O8H 2O), having prepared concentration is the solution 1000g of 0.06mol/l., to described solution in add borine-dimethyl amine complex compound (Northeast chemical company system) as reductive agent, make it to reach 0.08mol/l thereafter.
Then, under described metal oxide film being formed, flood described base material, use Naflon bubbler (Asone corporate system) to produce the bubble of air, bubble is supplied with to base material with 50 ℃ of certain conditions of solution maintenance temperature.At this moment, use solution circulated, make it by strainer by described metal oxide film is formed, and with the throw out or the dust eliminating of sneaking into.In addition, by using described UV irradiation equipment with uitraviolet intensity 20mW/cm to this kind base material 2Irradiation, and on described base material, obtained metal oxide film., with pure water clean thereafter, dry 1 hour down at 100 ℃.
Use described X-ray diffraction device to measure described metal oxide film, its result is to confirm to have formed zirconium oxide film.In addition, utilize photoelectron spectroscopy apparatus (V.G.Scientific corporate system, ESCALAB 200i-XL) to measure described metal oxide film, its result is to confirm to have formed zirconium oxide film.In addition, use scanning electron microscope (SEM) to measure the thickness of described metal oxide film, its result is 200nm.
[embodiment 5～37]
Among the embodiment 5～37, under the experiment condition shown in following table 1 and the table 2, on base material, formed metal oxide film.And the measuring method of the formation method transitivity of metal oxide film is according to embodiment 4.
And, so-called glass/TiO 2Base material is to be coated with TiO on glass with the paste shape 2The base material of particulate.As concrete manufacture method, at first, in water and Virahol as solvent, add titanium oxide microparticle (the Japanese Aerosil corporate system of one-level particle 20nm, P25), methyl ethyl diketone, polyoxyethylene glycol (molecular-weight average 3000), make it to reach respectively 37.5 weight %, 1.25 weight %, 1.88 weight %, the use homogenizer has been made dissolving, has been disperseed the slip of described sample.This slip utilization is scraped after the skill in using a kitchen knife in cookery coats on the glass baseplate, placed 20 minutes, dry 30 minutes down at 100 ℃.Next, use the electronics retort furnace (the Denken corporate system, P90) under 500 ℃, burnt till under the air atmosphere 30 minutes.So just obtained having the glass baseplate (glass/TiO of porous titanium oxide film 2).
In addition, as glass/ZrO 2The concrete manufacture method of base material, at first, in water and Virahol as solvent, adding BET conversion diameter is zirconium white particulate (Hosogawa corporate system), ethanol, the polyoxyethylene glycol (molecular-weight average 3000) of 37nm, make it to reach respectively 40 weight %, 1.5 weight %, 1.88 weight %, the use homogenizer has been made dissolving, has been disperseed the slip of described sample.This slip utilization is scraped after the skill in using a kitchen knife in cookery coats on the glass baseplate, placed 20 minutes, dry 15 minutes down at 100 ℃.Next, use the electronics retort furnace (the Denken corporate system, P90) under 500 ℃, burnt till under the air atmosphere 60 minutes.So just obtained having the glass baseplate (glass/ZrO of porous zirconia film 2Base material).
In addition, in embodiment 9 that has used metal complex as source metal and embodiment 11, used the mixed solvent of water 70vol%, Virahol 20vol% and toluene 10vol% as solvent.Using among the embodiment 10 of metal complex as solvent equally, used the mixed solvent of water 10vol%, Virahol 70vol% and toluene 20vol% as solvent, in embodiment 12, used the mixed solvent of Virahol 70vol% and toluene 30vol% as solvent.
And, in embodiment 4～37, among the embodiment beyond the described embodiment, used the mixed solvent of water 80vol% and Virahol 20vol%.
In addition, in embodiment 6,7,13,31,32,35,36, utilize photoelectron spectroscopy apparatus (V.G.Scientific corporate system, ESCALAB 200i-XL) can confirm to have formed metal oxide film.
In addition, experiment condition and the result with embodiment 4～37 is shown in table 1 and the table 2.
Table 1
Metal oxide film Source metal (mol/l) Reductive agent (mol/l) Assisting ion source (mol/l) Base material The liquid temperature (℃) Time Bubble UV (mW/cm 2) Thickness (nm) The film forming postheat treatment The XRD crystallinity ESCA
Embodiment 4 ZrO 2 ZrCl 2O·8H 2O 0.06 ③ 0.08 - - SUS 50 12h Air 20 200 - ○ ○
Embodiment 5 SnO 2 SnCl 2·2H 2O 0.03 ③ 0.01 - - Glass 60 1h - 20 100 - ○ ○
Embodiment 6 MgO MgBr 2·6H 2O 0.03 ① 0.01 - - Glass 60 24h - - 120 100℃5h × ○
Embodiment 7 SiO 2 (NH 4) 2SiF 6 0.01 ② 0.05 - - Silicon wafer 90 1h - - 200 - × ○
Embodiment 8 PbO 2 Pb(ClO 4) 2·3H 2O 0.05 ② 0.1 ① 0.03 Glass 60 1h - - 150 150℃1h ○ ○
Embodiment 9 TiO 2 (OH) 2Ti(C 3H 5O 2) 2 0.03 ③ 0.05 - - Glass/TiO 2 90 5h - - 150 - ○ ○
Embodiment 10 TiO 2 Ti(OC 3H 7) 4 0.03 ③ 0.1 - - Glass/TiO 2 60 12h - - 200 - ○ ○
Embodiment 11 TiO 2 Ti(C 3H 7O) 2(C 8H 9O 3) 2 0.03 ③ 0.05 - - Glass/ZrO 2 80 5h - - 120 - ○ ○
Embodiment 12 ZrO 2 Zr(CH 3COCHCOCH 3) 4 0.03 ③ 0.03 - - Glass 70 24h - - 100 - ○ ○
Embodiment 13 CaO CaCl 2·2H 2O 0.05 ④ 0.05 ② 0.03 Glass 90 30min Air - 80 - × ○
Embodiment 14 TiO 2 (C 3H 7O) 2Ti(C 5H 7O 2) 2 0.1 ③ 0.1 ③ 0.02 Glass 90 2h Air - 300 - ○ ○
Embodiment 15 In 2O 3 In(NO 3) 3·nH 2O 0.01 ③ 0.1 - - Glass 80 50min Air - 150 150℃1h ○ ○
Embodiment 16 In 2O 3 In(NO 3) 3·nH 2O 0.01 ③ 0.05 - - Glass/TiO 2 50 3min Air - 5 - ○ ○
Embodiment 17 La 2O 3 La(NO 3) 3·6H 2O 0.01 ④ 0.01 ② 0.01 Silicon wafer 90 1h Air - 120 400℃1h ○ ○
Embodiment 18 CeO 2 Ce(CH 3COO) 3·H 2O 0.05 ④ 0.15 - - Glass 80 1h Air - 380 - ○ ○
Embodiment 19 ITO In(NO 3) 3·nH 2O 0.01 ③ 0.03 - - Glass 80 1h Air - 150 - ○ ○
SnCl 2 0.005
Embodiment 20 Gd-CeO 2 Gd(NO 3) 3 0.02 ④ 0.05 - - Glass 90 1h Air - 80 - ○ ○
Ce(CH 3COO) 3·H 2O 0.005
Embodiment 21 Sm-CeO 2 Sm(NO 3) 3 0.02 ② 0.05 - - Glass 80 6h Air - 120 - ○ ○
Ce(CH 3COO) 3·H 2O 0.005
Reductive agent 1. Borine-tert-butylamine complex compound
② Borine-N, N-diethylbenzene amine complex
③ Borine-dimethyl amine complex compound
④ Borine-triethylamine complex compound
The assisting ion source 1. The chlorate ions
② The bromic acid ion
③ The hypobromous acid ion
④ The high chloro acid ion
The assisting ion source 5. The chlorous acid ion
⑥ Hypochlorite ion
⑦ Nitrate ion
⑧ Nitrite ion
Table 2
Metal oxide film Source metal (mol/l) Reductive agent (mol/l) Assisting ion source (mol/l) Base material The liquid temperature (℃) Time Bubble UV (mW/cm 2) Thickness (nm) The film forming postheat treatment The XRD crystallinity ESCA
Embodiment
22 Al 2O 3 AlCl 3 0.08 ② 0.1 ④ 0.01 Silicon wafer 65 24h Air - 60 1000℃ 1h ○ ○
Embodiment 23 V 2O 5 VCl 2 0.02 ③ 0.05 ⑦ 0.02 Glass 80 12h - - 150 500℃ 1h ○ ○
Embodiment 24 MnO 2 Mn(CH 3COO) 2·4H 2O 0.03 ② 0.03 ⑧ 0.02 The titanium plate 50 8h - - 300 100℃ 1h ○ ○
Embodiment 25 Fe 2O 3 Fe(ClO 4) 3·6H 2O 0.01 ③ 0.01 - - Silicon wafer 50 10h - 20 400 - ○ ○
Embodiment 26 Co 3O 4 Co(NO 3) 2·6H 2O 0.03 ① 0.03 - - - 80 24h - - 300 500℃ 1h ○ ○
Embodiment 27 NiO Ni(CH 3COO) 2·4H 2O 0.01 ② 0.02 ② 0.03 Glass/TiO 2 50 12h - 10 200 200℃ 1h ○ ○
Embodiment 28 CuO Cu(NO 3) 2·3H 2O 0.01 ④ 0.02 ④ 0 01 Glass/TiO 2 50 5h - - 100 400℃ 1h ○ ○
Embodiment 29 ZnO ZnCl 2 0.02 ② 0.02 ⑤ 0.03 Glass/TiO 2 70 2h - - 100 500℃ 1h ○ ○
Embodiment 30 Y 2O 3 Y(CH 3COO) 3·4H 2O 0.05 ④ 0.08 - - Glass/TiO 2 80 6h - 20 200 300℃ 1h ○ ○
Embodiment 31 AgO AgNO 3 0.01 ① 0.05 ⑧ 0.02 Glass 90 24h - - 50 500℃ 1h × ○
Embodiment 32 Sm 2O 3 Sm(NO 3) 3·6H 2O 0.06 ③ 0.07 ⑥ 0.05 Glass/TiO 2 60 10h Air - 40 500℃ 1h × ○
Embodiment 33 The La of Ga has mixed 2O 3 La(NO 3) 3·6H 2O 0.02 ③ 0.03 - - Silicon wafer 70 24h - - 80 500℃ 1h ○ ○
Ga(NO 3) 3 0.005
Embodiment 34 HfO 2 Hf(SO 4) 2 0.07 ① 0.1 ④ 0.05 SUS 60 24h - 10 80 400℃ 1h ○ ○
Embodiment 35 Sc 2O 3 Sc(NO 3) 3·4H 2O 0.07 ① 0.1 - - Glass/TiO 2 50 24h Air - 40 500℃ 1h × ○
Embodiment 36 Gd 2O 3 Gd(NO 3) 3·6H 2O 0.05 ④ 0.1 - - Glass/TiO 2 90 10h Air - 40 500℃ 1h × ○
Embodiment 37 NiO-YSZ Ni(CH 3COO) 2·4H 2O 0.03 ③ 0.05 - - Silicon wafer 60 24h - - 200 1000℃ 1h ○ ○
ZrO(NO 3) 2·2H 2O 0.03
YCl 3·6H 2O 0.01
Reductive agent 1. Borine-tert-butylamine complex compound
② Borine-N, N-diethylbenzene amine complex
③ Borine-dimethyl amine complex compound
④ Borine-triethylamine complex compound
The assisting ion source 1. The chlorate ions
② The bromic acid ion
③ The hypobromous acid ion
④ The high chloro acid ion
The assisting ion source 5. The chlorous acid ion
⑥ Hypochlorite ion
⑦ Nitrate ion
⑧ Nitrite ion

Claims (6)

1. the manufacture method of a metal oxide film is by making the metal oxide film that has dissolved metal-salt or metal complex as source metal form the manufacture method that obtains the metal oxide film of metal oxide film with solution contact substrate surface, it is characterized in that,
Described metal oxide film forms and contains reductive agent with solution.
2. the manufacture method of metal oxide film according to claim 1 is characterized in that, in described substrate surface and described metal oxide film being formed contact with solution, and mixed oxidization gas.
3. the manufacture method of metal oxide film according to claim 2 is characterized in that, described oxidizing gas is oxygen or ozone.
4. the manufacture method of metal oxide film according to claim 1 is characterized in that, in described substrate surface and described metal oxide film being formed contact with solution, and irradiation ultraviolet radiation.
5. according to the manufacture method of any described metal oxide film in the claim 1 to 4, it is characterized in that described metal oxide film forms and contains at least a metallic element that is selected from the group that is made of Mg, Al, Si, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Ag, In, Sn, Ce, Sm, Pb, La, Hf, Sc, Gd and Ta with source metal used in the solution.
6. according to the manufacture method of any described metal oxide film in the claim 1 to 5, it is characterized in that described metal oxide film forms and contains at least a ion species that is selected from the group that is made of chlorate ions, high chloro acid ion, chlorous acid ion, hypochlorite ion, bromic acid ion, hypobromous acid ion, nitrate ion and nitrite ion with solution.
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